Stabilizer mixtures

ABSTRACT

A stabilizer mixture containing  
     (A) a sterically hindered amine compound,  
     (B) an organic salt of Ca or an inorganic salt of Ca and  
     (C) an organic salt of Mg, an inorganic salt of Mg, an organic salt of Zn or an inorganic salt of Zn;  
     with the proviso that component (C) is Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite, when component (B) is calcium stearate.

[0001] The present invention relates to a stabilizer mixture containinga sterically hindered amine compound, a Ca compound and an Zn or Mgcompound, the use of this mixture for stabilizing a polyolefin againstdegradation induced by light, heat or oxidation and the polyolefin thusstabilized.

[0002] The stabilization of polyolefins is described in numerouspublications, for example in U.S. Pat. No. 4,929,652, U.S. Pat. No.5,025,051, U.S. Pat. No. 5,037,870, EP-A-276,923, EP-A-290,388,EP-A-429,731, EP-A-468,923, EP-A-565,184, EP-A-690,094, GB-A-2,252,324,DE-A-19,545,896 (Derwent 96-278,994/29; Chemical Abstracts 125:116779q),WO-A-95/25,767 and Chemical Abstracts 106:197407z.

[0003] In more detail, the present invention relates to a stabilizermixture containing

[0004] (A) a sterically hindered amine compound,

[0005] (B) an organic salt of Ca or an inorganic salt of Ca and

[0006] (C) an organic salt of Mg, an inorganic salt of Mg, an organicsalt of Zn or an inorganic salt of Zn;

[0007] with the proviso that component (C) is Mg-hydroxide-carbonate,Zn-hydroxide-carbonate or dolomite, when component (B) is calciumstearate.

[0008] Component (C) is in particular Mg-hydroxide-carbonate,Zn-hydroxide-carbonate or dolomite, when component (B) is an organicsalt of Ca.

[0009] The sterically hindered amine is preferably a compound containingat least one group of the formula (I) or (II)

[0010] in which G is hydrogen or methyl, and G₁ and G₂, independently ofone another, are hydrogen, methyl or together are a substituent ═O.

[0011] More detailed examples of sterically hindered amines aredescribed below under classes (a′) to (i′).

[0012] (a′) A compound of the formula (Ia)

[0013] in which n₁ is a number from 1 to 4, G and G₁, independently ofone another, are hydrogen or methyl,

[0014] G₁₁ is hydrogen, O⁻, hydroxyl, C₁-C₁₈alkyl, C₃-C₈alkenyl,C₃-C₈alkynyl, C₇-C₁₂aralkyl, C₁-C₁₈alkoxy, C₅-C₈cycloalkoxy,C₇-C₉phenylalkoxy, C₁-C₈alkanoyl, C₃-C₅alkenoyl, C₁-C₁₈alkanoyloxy,glycidyl or a group of the formula —CH₂CH(OH)-Z, in which Z is hydrogen,methyl or phenyl, G₁₁ preferably being H, C₁-C₄alkyl, allyl, benzyl,acetyl or acryloyl, and G₁₂, if n₁ is 1, is hydrogen, C₁-C₁₈alkyl whichis uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl,benzoyl, glycidyl, a monovalent radical or an aliphatic, cycloaliphatic,araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid orphosphorus-containing acid or a monovalent silyl radical, preferably aradical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, ofa cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or anα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms, where eachcarboxylic acid can be substituted in the aliphatic, cycloaliphatic oraromatic moiety by 1 to 3 -COOZ₁₂ groups, in which Z₁₂ is H,C₁-C₂₀alkyl, C₃-C₁₂alkenyl, C₅-C₇cycloalkyl, phenyl or benzyl,

[0015] G₁₂, if n₁ is 2, is C₂-C₁₂alkylene, C₄-C₁₂alkenylene, xylylene, adivalent radical of an aliphatic, cycloaliphatic, araliphatic oraromatic dicarboxylic acid, dicarbamic acid or phosphorus-containingacid or a divalent silyl radical, preferably a radical of an aliphaticdicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic oraromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic,cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms,where each dicarboxylic acid may be substituted in the aliphatic,cycloaliphatic or aromatic moiety by one or two -COOZ₁₂ groups, G₁₂, ifn₁ is 3, is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid, which may be substituted in the aliphatic,cycloaliphatic or aromatic moiety by -COOZ₁₂, of an aromatic tricarbamicacid or of a phosphorus-containing acid, or is a trivalent silylradical, and G₁₂, if n₁ is 4, is a tetravalent radical of an aliphatic,cycloaliphatic or aromatic tetracarboxylic acid.

[0016] The carboxylic acid radicals mentioned above are in each casetaken to mean radicals of the formula (—CO)_(x)R, where x is as definedabove, and the meaning of R arises from the definition given.

[0017] Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-hexadecyl or n-octadecyl.

[0018] C₃-C₈alkenyl G₁₁ can be, for example, 1-propenyl, allyl,methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or4-tert-butyl-2-butenyl.

[0019] C₃-C₈alkynyl G₁₁ is preferably propargyl.

[0020] C₇-C₁₂aralkyl G₁₁ is, in particular, phenethyl, especiallybenzyl.

[0021] C₁-C₁₈alkoxy G₁₁ is, for example, methoxy, ethoxy, propoxy,isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy,octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy andoctadecyloxy. C₆-C₁₂alkoxy, in particular heptoxy and octoxy, ispreferred.

[0022] C₅-C₈cycloalkoxy G₁₁ is, for example, cyclopentoxy, cyclohexoxy,cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.C₅-C₈cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, ispreferred.

[0023] C₇-C₉phenylalkoxy is, for example, benzyloxy.

[0024] C₁-C₈alkanoyl G₁₁ is, for example, formyl, propionyl, butyryl,octanoyl, but preferably acetyl and C₃-C₅alkenoyl G₁₁ is in particularacryloyl.

[0025] C₁-C₁₈alkanoyloxy G₁₁ is, for example, formyloxy, acetyloxy,propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy andstearoyloxy.

[0026] Examples of several G₁₂ radicals are given below.

[0027] If G₁₂ is a monovalent radical of a carboxylic acid, it is, forexample, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoylor β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

[0028] If G₁₂ is a monovalent silyl radical, it is, for example, aradical of the formula -(C_(j)H_(2j))—Si(Z′)₂Z″, in which j is aninteger in the range from 2 to 5, and Z′ and Z″, independently of oneanother, are C₁-C₄alkyl or C₁-C₄alkoxy.

[0029] If G₁₂ is a divalent radical of a dicarboxylic acid, it is, forexample, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl,maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl,butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl orbicycloheptenedicarbonyl radical or a group of the formula

[0030] If G₁₂ is a trivalent radical of a tricarboxylic acid, it is, forexample, a trimellitoyl, citryl or nitrilotriacetyl radical.

[0031] If G₁₂ is a tetravalent radical of a tetracarboxylic acid, it is,for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylicacid or of pyromellitic acid.

[0032] If G₁₂ is a divalent radical of a dicarbamic acid, it is, forexample, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

[0033] Preference is given to compounds of the formula (Ia) in which Gand G₁ are hydrogen, G₁₁ is hydrogen or methyl, n₁ is 2 and G₁₂ is thediacyl radical of an aliphatic dicarboxylic acid having 4-12 carbonatoms.

[0034] Examples of polyalkylpiperidine compounds from this class are thefollowing compounds:

[0035] 1) 4-hydroxy-2,2,6,6-tetramethylpiperidine

[0036] 2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

[0037] 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

[0038] 4)1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine

[0039] 5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine

[0040] 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine

[0041] 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine

[0042] 8) 1,2,2,6,6-pentamethylpiperidin-4-ylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

[0043] 9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate

[0044] 10) di(2,2,6,6-tetramethylpiperidin-4-yl) succinate

[0045] 11) di(2,2,6,6-tetramethylpiperidin-4-yl) glutarate

[0046] 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate

[0047] 13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate

[0048] 14) di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate

[0049] 15) di(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate

[0050] 16) di(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate

[0051] 17) 1-hydroxy-4-β-cyanoethoxy-2,2,6,6-tetramethylpiperidine

[0052] 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate

[0053] 19) tri(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate

[0054] 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine

[0055] 21) di(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate

[0056] 22) di(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate

[0057] 23) di(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate

[0058] 24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

[0059] 25) di(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate

[0060] 26)hexane-1′,6′-bis(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)

[0061] 27)toluene-2′,4′-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)

[0062] 28) dimethylbis(2,2,6,6-tetramethylpiperidin-4-oxy)silane

[0063] 29) phenyltris(2,2,6,6-tetramethylpiperidin-4-oxy)silane

[0064] 30) tris(1 -propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite

[0065] 30-a) tris(1 -methyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite

[0066] 31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate

[0067] 32) phenyl bis(1,2,2,6,6-pentamethylpiperidin-4-yl) phosphonate

[0068] 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine

[0069] 34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine

[0070] 35) 4-hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine

[0071] 36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

[0072] 36-a)1,2,3,4-tetrakis[2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl]butane

[0073] 36-b)1,2,3,4-tetrakis[1,2,2,6,6-pentamethylpiperidin-4-yloxycarbonyl]butane

[0074] 36-c) 2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl(C₁₅-C₁₇alkane)

[0075] (b′) A compound of the formula (Ib)

[0076] in which n₂ is the number 1, 2 or 3, G, G₁ and G₁₁ are as definedunder (a′), G₁₃ is hydrogen, C₁-C₁₂alkyl, C₂-C₅hydroxyalkyl,C₅-C₇cycloalkyl, C₇-C₈aralkyl, C₁-C₁₈alkanoyl, C₃-C₅alkenoyl, benzoyl ora group of the formula

[0077] and G₁₄, if n₂ is 1, is hydrogen, C₁-C₁₈alkyl, C₃-C₈alkenyl,C₅-C₇cycloalkyl, C₁-C₄alkyl which is substituted by a hydroxyl, cyano,alkoxycarbonyl or carbamide group, glycidyl, a group of the formula—CH₂—CH(OH)-Z or of the formula —CONH-Z, in which Z is hydrogen, methylor phenyl;

[0078] G₁₄, if n₂ is 2, is C₂-C₁₂alkylene, C₆-C₁₂arylene, xylylene, a—CH₂—CH(OH)—CH₂ group or a —CH₂—CH(OH)—CH₂—O-D—O— group, in which D isC₂-C₁₀alkylene, C₆-C₁₅arylene, C₆-C₁₂cycloalkylene, or, provided thatG₁₃ is not alkanoyl, alkenoyl or benzoyl, G₁₄ can alternatively be1-oxo-C₂-C₁₂alkylene, a divalent radical of an aliphatic, cycloaliphaticor aromatic dicarboxylic acid or dicarbamic acid or alternatively thegroup —CO—, G₁₄, if n₂ is 3, is a group

[0079] or, if n₂ is 1, G₁₃ and G₁₄ together can be the divalent radicalof an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylicacid.

[0080] Some examples for the radicals G₁₃, G₁₄ and D are given below.

[0081] Any alkyl substituents are as defined above for (a′).

[0082] Any C₅-C₇cycloalkyl substituents are, in particular, cyclohexyl.

[0083] C₇-C₈aralkyl G₁₃ is, in particular, phenylethyl or especiallybenzyl.

[0084] C₂-C₅hydroxyalkyl G₁₃ is, in particular, 2-hydroxyethyl or2-hydroxypropyl.

[0085] C₁-C₁₈alkanoyl G₁₃ is, for example, formyl, acetyl, propionyl,butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, butpreferably acetyl, and C₃-C₅alkenoyl G₁₃ is, in particular, acryloyl.

[0086] C₂-C₈alkenyl G₁₄ is, for example, allyl, methallyl, 2-butenyl,2-pentenyl, 2-hexenyl or 2-octenyl.

[0087] G₁₄ as a hydroxyl-, cyano-, alkoxycarbonyl- orcarbamide-substituted C₁-C₄alkyl can be, for example, 2-hydroxyethyl,2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl,2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or2-(dimethylaminocarbonyl)ethyl.

[0088] Any C₂-C₁₂alkylene radicals are, for example, ethylene,propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene,octamethylene, decamethylene or dodecamethylene.

[0089] Any C₆-C₁₅arylene substituents are, for example, o-, m- orp-phenylene, 1,4-naphthylene or 4,4′-diphenylene.

[0090] C₆-C₁₂cycloalkylene is, in particular, cyclohexylene.

[0091] G₁₄ as 1 -oxo-C₂-C₁₂alkylene is preferably a group

[0092] Preference is given to compounds of the formula (Ib) in which n₂is 1 or 2, G and G₁ are hydrogen, G₁₁ is hydrogen or methyl, G₁₃ ishydrogen, C₁-C₁₂alkyl or a group of the formula

[0093] and G₁₄, in the case where n=1, is hydrogen or C₁-C₁₂alkyl, and,in the case where n=2, is C₂-C₈alkylene or 1 -oxo-C₂-C₈alkylene.

[0094] Examples of polyalkylpiperidine compounds from this class are thefollowing compounds:

[0095] 37)N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diamine

[0096] 38)N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diacetamide

[0097] 39) bis(2,2,6,6-tetramethylpiperidin-4-yl)amine

[0098] 40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine

[0099] 41)N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-dibutyladipamide

[0100] 42)N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-dicyclohexyl-2-hydroxypropylene-1,3-diamine

[0101] 43) N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine

[0102] 44) N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)succinamide

[0103] 45) bis(2,2,6,6-tetramethylpiperidin-4-yl)N-(2,2,6,6-tetramethylpiperidin-4-yl)-β-aminodipropionate

[0104] 46) The compound of the formula

[0105] 47) 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine

[0106] 48)4-(3-methyl-4-hydroxy-5-tert-butyl-benzamido)-2,2,6,6-tetramethylpiperidine

[0107] 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine

[0108] 49-b)N.N′,N″-tris[2,2,6,6-tetramethylpiperidin-4-ylamino(2-hydroxypropylene)]isocyanurate

[0109] 49-c)2-(2,2,6,6-tetramethylpiperidin-4-ylamino)-2-(2,2,6,6-tetramethylpiperidin-4-ylaminocarbonyl)propane

[0110] 49-d)1,6-bis[N-(2,2,6,6-tetramethylpiperidin-4-yl)formylamino]hexane

[0111] (c′) A compound of the formula (Ic)

[0112] in which n₃ is the number 1 or 2, G, G₁ and G₁₁ are as definedunder (a′), and G₁₅, if n₃ is 1, is C₂-C₈alkylene, C₂-C₈hydroxyalkyleneor C₄-C₂₂acyloxyalkylene, and if n₃ is 2, G₁₅ is the (—CH₂)₂C(CH₂—)₂group.

[0113] C₂-C₈alkylene or C₂-C₈hydroxyalkylene G₁₅ is, for example,ethylene, 1-methylethylene, propylene, 2-ethylpropylene or2-ethyl-2-hydroxymethylpropylene.

[0114] C₄-C₂₂acyloxyalkylene G₁₅ is, for example,2-ethyl-2-acetoxymethylpropylene.

[0115] Examples of polyalkylpiperidine compounds from this class are thefollowing compounds:

[0116] 50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane

[0117] 51)9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane

[0118] 52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane

[0119] 53)9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]undecane

[0120] 54)9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]-undecane

[0121] 55)2,2,6,6-tetramethylpiperidine-4-spiro-2′-(1′,3″-dioxane)-5′-spiro-5″-(1″,3′-dioxane)-2″-spiro-4′″-(2′″,2′″,6′″,6′″-tetramethylpiperidine)

[0122] (d′) A compound of the formula (Id-1), (Id-2) or (Id-3),

[0123] in which n₄ is the number 1 or 2, G, G₁ and G₁₁ are as definedunder (a′), G₁₆ is hydrogen, C₁-C₁₂alkyl, allyl, benzyl, glycidyl orC₂-C₆alkoxyalkyl, and G₁₇, if n₄ is 1, is hydrogen, C₁-C₁₂alkyl,C₃-C₅alkenyl, C₇-C₉aralkyl, C₅-C₇cycloalkyl, C₂-C₄hydroxyalkyl,C₂-C₆alkoxyalkyl, C₆-C₁₀aryl, glycidyl or a group of the formula—(CH₂)_(p)—COO-Q or —(CH₂)_(p)—O—CO-Q, in which p is 1 or 2, and Q isC₁-C₄alkyl or phenyl, and G₁₇, if n is 2, is C₂-C₁₂alkylene,C₄-C₁₂alkenylene, C₆-C₁₂arylene, a group of the formula—CH₂—CH(OH)—CH₂-O-D′—O—CH₂—CH(OH)—CH₂—, in which D′ is C₂-C₁₀alkylene,C₆-C₁₅arylene, C₆-C₁₂cycloalkylene or a group of the formula—CH₂CH(OD″)CH₂—(OCH₂—CH(OD″)CH₂)₂—, in which D″ is hydrogen,C₁-C₁₈alkyl, allyl, benzyl, C₂-C₁₂alkanoyl or benzoyl, T₁ and T₂,independently of one another, are hydrogen, C₁-C₁₈alkyl or unsubstitutedor halogen- or C₁-C₄alkyl-substituted C₆-C₁₀aryl or C₇-C₉aralkyl, or T₁and T₂ together with the carbon atom bonding them form aC₅-C₁₄cycloalkane ring.

[0124] A compound of the formula (Id-3) is preferred.

[0125] Some examples of the several variables in the formulae (Id-1),(Id-2) and (Id-3) are given below.

[0126] Any C₁-C₁₂alkyl substituents are, for example, methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

[0127] Any C₁-C₁₈alkyl substituents can be, for example, theabovementioned groups and in addition, for example, n-tridecyl,n-tetradecyl, n-hexadecyl or n-octadecyl.

[0128] Any C₂-C₆alkoxyalkyl substituents are, for example,methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl,ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl,isopropoxyethyl or propoxypropyl.

[0129] C₃-C₅alkenyl G₁₇ is, for example, 1-propenyl, allyl, methallyl,2-butenyl or 2-pentenyl.

[0130] C₇-C₉aralkyl G₁₇, T₁ and T₂ are, in particular, phenethyl orespecially benzyl. If T₁ and T₂ together with the carbon atom form acycloalkane ring, this can be, for example, a cyclopentane, cyclohexane,cyclooctane or cyclododecane ring.

[0131] C₂-C₄hydroxyalkyl G₁₇ is, for example, 2-hydroxyethyl,2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

[0132] C₆-C₁₀aryl G₁₇, T₁ and T₂ are, in particular, phenyl or a- or,-naphthyl, which are unsubstituted or substituted by halogen orC₁-C₄alkyl.

[0133] C₂-C₁₂alkylene G₁₇ is, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

[0134] C₄-C₁₂alkenylene G₁₇ is, in particular, 2-butenylene,2-pentenylene or 3-hexenylene.

[0135] C₆-C₁₂arylene G₁₇ is, for example, o-, m- or p-phenylene,1,4-naphthylene or 4,4′-diphenylene.

[0136] C₂-C₁₂alkanoyl D″ is, for example, propionyl, butyryl, octanoyl,dodecanoyl, but preferably acetyl.

[0137] C₂-C₁₀alkylene, C₆-C₁₅arylene or C6-C₁₂cycloalkylene D′ have, forexample, one of the definitions given for D under (b′).

[0138] Examples of polyalkylpiperidine compounds from this class are thefollowing compounds:

[0139] 56)3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

[0140] 57)3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

[0141] 58)3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione

[0142] 59)3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione

[0143] 60)1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione

[0144] 61)2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane

[0145] 62)2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane

[0146] 63)2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane

[0147] 64)2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane andpreferably:

[0148] 65)8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

[0149] and the compounds of the following formulae:

[0150] 66)

[0151] 67)

[0152] 68)

[0153] 69-a)

[0154] 69-b) Mixture of 60% by weight of

[0155] and 40% by weight of

[0156] (e′) A compound of the formula (Ie)

[0157] in which n₅ is the number 1 or 2, and G₁₈ is a group of theformula

[0158] in which G and G₁₁ are as defined under (a′), and G₁ and G₂ arehydrogen, methyl or, together, are a substituent ═O,

[0159] E is —O— or -ND′″-,

[0160] A is C₂-C₆alkylene or —(CH₂)₃—O— and

[0161] x₁ is the number 0 or 1,

[0162] D′″ is hydrogen, C₁-C₁₂alkyl, C₂-C₅hydroxyalkyl orC₅-C₇cycloalkyl,

[0163] G₁₉ is identical to G₁₈ or is one of the groups —N(G₂₁)(G₂₂),-OG₂₃, —N(H)(CH₂OG₂₃) or —N(CH₂OG₂₃)₂,

[0164] G₂₀, if n=1, is identical to G₁₈ or G₁₉ and, if n=2, is an-E-D^(IV)-E- group, in which D^(IV) is C₂-C₈alkylene or C₂-C₈alkylenewhich is interrupted by 1 or 2 -NG₂₁- groups,

[0165] G₂₁ is C₁-C₁₂alkyl, cyclohexyl, benzyl or C₁-C₄-hydroxyalkyl or agroup of the formula

[0166] G₂₂ is C₁-C₁₂alkyl, cyclohexyl, benzyl or C₁-C₄hydroxyalkyl, andG₂₃ is hydrogen, C₁-C₁₂alkyl or phenyl, or G₂₁, and G₂₂ together areC₄-C₅alkylene or C₄-C₅oxaalkylene, for example —CH₂CH₂—O—CH₂CH₂—, or agroup of the formula —CH₂CH₂—N(G₁₁)—CH₂CH₂—.

[0167] Some examples of the several variables in the formula (Ie) aregiven below.

[0168] Any C₁-C₁₂alkyl substituents are, for example, methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

[0169] Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4- hydroxybutyl.

[0170] Any C₅-C₇cycloalkyl substituents are, for example, cyclopentyl,cyclohexyl or cycloheptyl. Cyclohexyl is preferred.

[0171] C₂-C₆alkylene A is, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene or hexamethylene.

[0172] If G₂₁ and G₂₂ together are C₄-C₅alkylene or oxaalkylene, theyare, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

[0173] Examples of polyalkylpiperidine compounds from this class are thecompounds of the following formulae:

[0174] 70)

[0175] 71)

[0176] 72)

[0177] 73)

[0178] 74)

[0179] where R is

[0180] 75)

[0181] where R has the same meaning as in compound 74.

[0182] 76)

[0183] where R′ is

[0184] 77)

[0185] where R′ has the same meaning as in compound 76.

[0186] 79)

[0187] 80)

[0188] (f′) A compound of the formula (If)

[0189] wherein G₁₁ is as defined under (a′).

[0190] A preferred example from this class is the following compound:

[0191] 80-a)

[0192] (g′) Oligomeric or polymeric compounds whose recurring structuralunit contains a 2,2,6,6-tetraalkylpiperidinyl radical, in particularpolyesters, polyethers, polyamides, polyamines, polyurethanes,polyureas, polyaminotriazines, poly(meth)acrylates,poly(meth)acrylamides and copolymers thereof which contain suchradicals.

[0193] Examples of 2,2,6,6-polyalkylpiperidine compounds from this classare the compounds of the following formulae, where m₁ to m₁₄ is a numberfrom 2 to about 200, preferably 2 to 100, for example 2 to 50, 2 to 40or 3 to 40 or 4 to 10.

[0194] The meanings of the end groups which saturate the free valencesin the oligomeric or polymeric compounds listed below depend on theprocesses used for the preparation of said compounds. The end groups canalso in addition be modified after the synthesis of the compounds.

[0195] 81)

[0196] 82)

[0197] In the compounds 81 and 82, the end group bonded to the —O— canbe, for example, hydrogen or a group —CO—(CH₂)₂—COO—Y or—CO—(CH₂)₄—COO—Y, respectively, with Y being hydrogen or C₁-C₄alkyl andthe end group bonded to the diacyl can be, for example, —O—Y or a group

[0198] 83)

[0199] In the compound 83, the end group bonded to the amino residue canbe, for example, a group

[0200] and the end group bonded to the diacyl residue can be, forexample, Cl.

[0201] 84-1)

[0202] 84-2)

[0203] In the compounds 84-1 and 84-2, the end group bonded to thetriazine residue can be, for example, chlorine or a group

[0204] and the end group bonded to the diamino group can be, forexample, hydrogen or a group

[0205] It may be convenient to replace the chlorine attached to thetriazine by e.g. —OH or an amino group. Suitable amino groups aretypically: pyrrolidin-1-yl, morpholino, —NH₂, —N(C₁-C₈alkyl)₂ and—NY′(C₁-C₈alkyl) wherein Y″ is hydrogen or a group of the formula

[0206] In the compound 85, the end group bonded to the2,2,6,6-tetramethylpiperidin-4-ylamino residue can be, for example,hydrogen and the end group bonded to the 2-hydroxypropylene residue canbe, for example,

[0207] 86)

[0208] In the compound 86, the end group bonded to the —O— can be, forexample, hydrogen or

[0209] and the end group bonded to the diacyl residue can be, forexample, —OCH₃ or Cl.

[0210] 87)

[0211] In the compound 87, the end group bonded to the —O— can be, forexample, hydrogen or

[0212] and the end group bonded to the diacyl radical can be, forexample, —OCH₃ or Cl.

[0213] 88)

[0214] In the compound 88, the end group bonded to the —O— can be, forexample, hydrogen or

[0215] and the end group bonded to the diacyl radical can be, forexample, —OCH₃ or Cl.

[0216] 89)

[0217] In the compound 89, the end group bonded to the —CH₂— can be, forexample, hydrogen and the end group bonded to the ester residue can be,for example,

[0218] 90)

[0219] In the compound 90, the end group bonded to the —CH₂— can be, forexample, hydrogen and the end group bonded to the ester residue can be,for example,

[0220] 91)

[0221] In the compound 91, the end group bonded to the —CH₂— can be, forexample, hydrogen and the end group bonded to the amide residue can be,for example,

[0222] 92)

[0223] In the compound 92, the end group bonded to the triazine residuecan be, for example, chlorine or a group

[0224] and the end group bonded to the diamino residue can be, forexample, hydrogen or a group

[0225] It may be convenient to replace the chlorine attached to thetriazine by e.g. —OH or an amino group. Suitable amino groups aretypically: pyrrolidin-1-yl, morpholino, —NH₂, —N(C₁-C₈alkyl)₂ and—NY′(C₁-C₈alkyl) wherein Y′ is hydrogen or a group of the formula

[0226] Preferred is also a compound which corresponds to compound 92wherein the 2,2,6,6-tetramethyl-4-piperidyl groups are replaced by1,2,2,6,6-pentamethyl-4-piperidyl groups.

[0227] 93)

[0228] In the compound 93, the end group bonded to the diamino residuecan be, for example, hydrogen and the end group bonded to the —CH₂CH₂—residue can be, for example,

[0229] 94)

[0230] In the compound 94, the end group bonded to the diamino residuecan be, for example, hydrogen and the end group bonded to the diacylresidue can be, for example, Cl.

[0231] 95)

[0232] in which R″ is a group of the formula

[0233] or the chain branching

[0234] R′″ is a group of the formula (95-I), and m′₁₅ and m″₁₅ are eacha number from 0 to 200, preferably 0 to 100, in particular 0 to 50, withthe proviso that m′₁₅+m″₁₅ is a number from 2 to 200, preferably 2 to100, in particular 2 to 50. In the compound 95, the end group bonded tothe diamino residue can be, for example, hydrogen and the end groupbonded to the —CH₂CH₂— group can be, for example, halogen, in particularCl or Br.

[0235] Further examples for polymeric compounds are:

[0236] 1) A compound of the formula (96-I) or (96-II)

[0237] wherein m₁₆ and m₁₆* are a number from 2 to 50.

[0238] During the preparation, the compounds of the formulae (96-I) and(96-II) can be obtained together as a mixture and therefore, can also beemployed as such. The (96-I):(96-II) weight ratio is, for example, from20:1 to 1:20 or from 1:10 to 10:1.

[0239] In the compounds of the formula (96-I), the terminal group bondedto the nitrogen can be, for example, hydrogen and the terminal groupbonded to the 2-hydroxypropylene radical can be, for example, a

[0240] group.

[0241] In the compounds of the formula (96-II), the terminal groupbonded to the dimethylene radical can be, for example, —OH, and theterminal group bonded to the oxygen can be, for example, hydrogen. Theterminal groups can also be polyether radicals.

[0242] 2) A compound of the formula (97)

[0243] wherein G₂₄, G₂₅, G₂₆, G₂₇ and G₂₈, independently of one another,are a direct bond or C₁-C₁₀alkylene, G₁₁ is as defined under (a′) andm₁₇ is a number from 1 to 50.

[0244] In the compound of the formula (97), the end group bonded tothe >C═O group can be, for example,

[0245] and the end group bonded to the oxygen can be, for example

[0246] Preferred are the following two compounds:

[0247] wherein the mean value of m₁₇ is 2.5.

[0248] 3) A compound of the formula (98)

[0249] in which approximately one third of the radicals R^(IV) are —C₂H₅and the others are a group

[0250] and m₁₈ is a number in the range from 2 to 200, preferably 2 to100, in particular 2 to 50.

[0251] In the compound (98), the end group bonded to the —CH₂— residuecan be, for example, hydrogen and the end group bonded to the—CH(CO₂R^(IV))— residue can be, for example, —CH═CH—COOR^(IV).

[0252] 4) A compound of the formula (99)

[0253] in which G₁₁ is as defined under (a′), G₂₉ and G₃₂, independentlyof one another, are a direct bond or a —N(X₁)—CO-X₂—CO—N(X₃)— group,where X₁ and X₃, independently of one another, are hydrogen, C₁-C₈alkyl,C₅-C₁₂cycloalkyl, phenyl, C₇-C₉phenylalkyl or a group of the formula(99-I)

[0254] and X₂ is a direct bond or C₁-C₄alkylene, G₃₀, G₃₁, G₃₄ and G₃₅,independently of one another, are hydrogen, C₁-C₃₀alkyl,C₅-C₁₂cycloalkyl or phenyl, G₃₃ is hydrogen, C₁-C₃₀alkyl,C₅-C₁₂cycloalkyl, C₇-C₉phenylalkyl, phenyl or a group of the formula(99-1), and m₁₉ is a number from 1 to 50.

[0255] In the compounds of the formula (99), the end group bonded to the2,5-dioxopyrrolidine ring can be, for example, hydrogen, and the endgroup bonded to the —C(G₃₄)(G₃₅)— radical can be, for example,

[0256] Examples of the compounds of the formula (99) are:

[0257] wherein G₁₁ is hydrogen or methyl, and m₁₉ is a number from 1 to25.

[0258] 5) A product obtainable by reacting an intermediate product,obtained by reaction of a polyamine of the formula (100a) with cyanuricchloride, with a compound of the formula (100b)

[0259] in which m′₂₀, m″₂₀ and m′″₂₀, independently of one another, area number from 2 to 12, G₃₆ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl,phenyl or C₇-C₉phenylalkyl, and G₁₁ is as defined under (a′). Apreferred product has the Chemical Abstracts-CAS No. 136 504-96-6(Compound 100-A).

[0260] In general, the above reaction product can be represented forexample by a compound of the formula 100-1, 100-2 or 100-3. It can alsobe in the form of a mixture of these three compounds.

[0261] A preferred meaning of the formula (100-1) is

[0262] A preferred meaning of the formula (100-2) is

[0263] A preferred meaning of the formula (100-3) is

[0264] In the above formulae 100-1 to 100-3, m₂₀ is preferably 1 to 20.

[0265] 6) A compound of the formula (101)

[0266] in which G₁₁ is as defined under (a′), G₃₇ is C₁-C₁₀alkyl,C₅-C₁₂cycloalkyl, C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl orC₁-C₁₀alkyl-substituted phenyl, G₃₈ is C₃-C₁₀alkylene and m₂₁ is anumber from 1 to 50.

[0267] In the compounds of the formula (101), the terminal group bondedto the silicon atom can be, for example, (G₃₇)₃Si—O—, and the terminalgroup bonded to the oxygen can be, for example, —Si(G₃₇)₃.

[0268] The compounds of the formula (101) can also be in the form ofcyclic compounds if m₂₁ is a number from 3 to 10, i.e. the free valencesshown in the structural formula then form a direct bond.

[0269] An example of a compound of the formula (101) is

[0270] with m₁₂ being a number from 1 to 20.

[0271] In the above shown oligomeric and polymeric compounds, examplesof alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethyl-hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,eicosyl and docosyl; examples of cycloalkyl are cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl; an example of C₇-C₉phenylalkyl is benzyl;and examples of alkylene are ethylene, propylene, trimethylene,tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene,trimethylhexamethylene, octamethylene and decamethylene.

[0272] (h′) A compound of the formula (Ih)

[0273] in which n₆ is the number 1 or 2, G and G₁₁ are as defined under(a′), and G₁₄ is as defined under (b′), but G₁₄ cannot be —CONH-Z and—CH₂—CH(OH)—CH₂—O-D—O—.

[0274] Examples of such compounds are the following:

[0275] (i′) A compound of the formula (Ii)

[0276] wherein the radicals G₃₉, independently of one another, are agroup of the formula (Ii-1)

[0277] in which G₄₀ is C₁-C₁₂alkyl or C₅-C₁₂cycloalkyl, G₄₁ isC₂-C₁₂alkylene and G₄₂ is hydrogen, C₁-C₈alkyl, —O⁻, —CH₂CN,C₃-C₆alkenyl, C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted onthe phenyl radical by C₁-C₄alkyl; or C₁-C₈acyl.

[0278] Alkyl is for example C₁-C₄alkyl, in particular methyl, ethyl,propyl or butyl.

[0279] Cycloalkyl is preferably cyclohexyl.

[0280] Alkylene is for example ethylene, propylene, trimethylene,tetramethylene, pentamethylene, 2,2-dimethyltrimethylene orhexamethylene.

[0281] Alkenyl is preferably allyl.

[0282] Phenylalkyl is preferably benzyl.

[0283] Acyl is preferably acetyl.

[0284] Examples of compounds from this class are the compounds of thefollowing formulae:

[0285] The sterically hindered amine compound (component (A)) ispreferably one of the above compounds 1 to 106. The compounds 5, 10, 13,14, 24, 25, 36-a, 36-b, 36-d, 49-a-I, 49-e, 63, 75, 76, 80-a, 81, 84-1,84-2, 92, 93, 96-I, 96-II, 97-I, 97-II, 99-I, 100-A, 101-I, 105 and 106are of interest. The compounds 13, 14, 36-a, 36-b, 36-d, 76, 81, 84-I,96-I, 96-II, 100-A, 101-I, 105 and 106 are preferred. The compounds 13,14, 36-d, 81, 84-1, 96-I, 96-II, 100-A, 101-I, 105 and 106 areparticularly preferred.

[0286] Examples of an organic salt of Ca are Ca-stearate, Ca-laurate,Ca-lactate and Ca-stearoyl-lactate.

[0287] Examples of an inorganic salt of Ca are CaO and Ca(OH)₂.

[0288] The organic salt of zinc or magnesium defined in component (C) ispreferably a compound of the formula MeL₂ in which Me is zinc ormagnesium and L is an anion of an organic acid or of an enol. Theorganic acid can, for example, be a sulfonic acid, sulfinic acid,phosphonic acid or phosphinic acid, but is preferably a carboxylic acid.The acid can be aliphatic, aromatic, araliphatic or cycloaliphatic; itcan be linear or branched; it can be substituted by hydroxyl or alkoxygroups; it can be saturated or unsaturated and it preferably contains 1to 24 carbon atoms.

[0289] Examples of carboxylic acids of this type are formic, acetic,propionic, butyric, isobutyric, caprioic, 2-ethylcaproic, caprylic,capric, lauric, palmitic, stearic, behenic, oleic, lactic, ricinoleic,2-ethoxypropionic, benzoic, salicylic, 4-butylbenzoic, toluic,4-dodecylbenzoic, phenylacetic, naphthylacetic, cyclohexanecarboxylic,4-butylcyclohexanecarboxylic or cyclohexylacetic acid. The carboxylicacid can also be a technical mixture of carboxylic acids, for exampletechnical mixtures of fatty acids or mixtures of alkylated benzoicacids.

[0290] Examples of organic acids containing sulfur or phosphorus aremethanesulfonic, ethanesulfonic, α,α-dimethylethanesulfonic,n-butanesulfonic, n-dodecanesulfonic, benzenesulfonic, toluenesulfonic,4-nonylbenzenesulfonic, 4-dodecylbenzenesulfonic or cyclohexanesulfonicacid, dodecanesulfinic, benzenesulfinic or naphthalenesulfinic acid,butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethylphenylphosphonate, monobutyl benzylphosphonate, dibutylphosphinic acidor diphenylphosphinic acid.

[0291] If L is an enolate anion, it is preferably an anion of aβ-dicarbonyl compound or of an o-acylphenol. Examples of β-dicarbonylcompounds are acetylacetone, benzoylacetone, dibenzoylmethane, ethylacetoacetate, butyl acetoacetate, lauryl acetoacetate orα-acetylcyclohexanone. Examples of o-acylphenols are 2-acetylphenol,2-butyroylphenol, 2-acetyl-1-naphthol, 2-benzoylphenol orsalicylaldehyde. The enolate is preferably the anion of a β-dicarbonylcompound having 5 to 20 carbon atoms.

[0292] Organic salts of zinc or magnesium are preferably anacetylacetonate or an aliphatic monocarboxylate having, for example, 1to 24 carbon atoms. Magnesium acetate, laurate and stearate, zincformate, acetate, oenanthate, laurate and stearate as well as zincacetylacetonate and magnesium acetylacetonate are some of the particularpreferred examples.

[0293] Zinc stearate, magnesium stearate, zinc laurate, magnesiumlaurate, zinc acetylacetonate, magnesium acetylacetonate, zinc acetateand magnesium acetate are of special interest.

[0294] The inorganic salt of zinc or magnesium is for example zincoxide, magnesium oxide, zinc hydroxide, magnesium hydroxide, or acarbonate containing compound such as

[0295] Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite, e.g aCa/Mg carbonate such as ®Microdol Super from ®Micro Minerals; or

[0296] a natural or synthetic hydrotalcite.

[0297] The natural hydrotalcite is held to possess a structureMg₆Al₂(OH)₁₆CO₃·4 H₂O. A typical empirical formula of a synthetichydrotalcite is

[0298] Al₂Mg_(4.35)OH_(11.36)CO_(3(1.67))·×H₂O.

[0299] Examples of the synthetic product include:

[0300] Mg_(0.7)Al_(0.3)(OH)₂(CO₃)_(0.15)·0.54 H₂O,

[0301] Mg_(4.5)Al₂(OH)₁₃CO₃·3.5 H₂O, or

[0302] Mg_(4.2)Al(OH)_(12.4)CO₃.

[0303] Preferred synthetic hydrotalcites are L-55R®II from ®REHEIS aswell as ®ZHT-4A and ®DHT-4A from ®Kyowa Chemical Industry Co.

[0304] A preferred embodiment of this invention relates to a stabilizermixture wherein component (C) is hydrotalcite, dolomite,Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, Zn-oxide, Mg-oxide,Zn-hydroxide, Mg-hydroxide, Zn-stearate, Mg-stearate, Zn-laurate,Mg-laurate, Zn-acetylacetonate, Mg-acetylacetonate, Zn-acetate orMg-acetate.

[0305] The following combinations of components (B) and (C) areparticularly preferred:

[0306] Ca oxide and Mg stearate

[0307] Ca oxide and Zn stearate

[0308] Ca oxide and hydrotalcite (®DHT-4A)

[0309] Ca hydroxide and Mg stearate

[0310] Ca hydroxide and Zn stearate

[0311] A further preferred embodiment of this invention relates to astabilizer mixture containing additionally

[0312] (D1) a pigment or

[0313] (D2) an UV absorber or

[0314] (D3) a pigment and an UV absorber.

[0315] The pigment (component (D1)) may be an inorganic or organicpigment.

[0316] Examples of inorganic pigments are titanium dioxide, zinc oxide,carbon black, cadmium sulfide, cadmium selenide, chromium oxide, ironoxide, lead oxide and so on.

[0317] Examples of organic pigments are azo pigments, anthraquinones,phthalocyanines, tetrachloroisoindolinones, quinacridones, isoindolines,perylenes, pyrrolopyrroles (such as Pigment Red 254) and so on.

[0318] All pigments described in “Gächter/Müller: Plastics AdditivesHandbook, 3rd Edition, Hanser Publishers, Munich Vienna New York”, page647 to 659, point 11.2.1.1 to 11.2.4.2 can be used as component (D1).

[0319] A particularly preferred pigment is titanium dioxide, optionallyin combination with an organic pigment.

[0320] Examples of such organic pigments are:

[0321] C.I. (Colour Index) Pigment Yellow 93, C.I. Pigment Yellow 95,C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow155, C.I. Pigment Yellow 162, C.I. Pigment Yellow 168, C.I. PigmentYellow 180, C.I. Pigment Yellow 183, C.I. Pigment Red 44, C.I. PigmentRed 170, C.I. Pigment Red 202, C.I. Pigment Red 214, C.I. Pigment Red254, C.I. Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Red 48:2,C.I. Pigment Red 48:3, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1,C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:3 andC.I. Pigment Violet 19.

[0322] Examples of the UV absorber (component (D2)) are a2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an ester ofsubstituted or unsubstituted benzoic acid, an acrylate, an oxamide, a2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or aformamidine.

[0323] The 2-(2′-hydroxyphenyl)benzotriazole is e.g.2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl- 2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,mixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonyl-ethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]or the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO(CH₂)₃—]₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

[0324] 2-(3′,5′-Di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole and2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)-benzotriazole are preferred.

[0325] The 2-hydroxybenzophenone is for example the 4-hydroxy,4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy or 2′-hydroxy-4,4′-dimethoxy derivatives.

[0326] 2-Hydroxy-4-octyloxybenzophenone is preferred.

[0327] The ester of a substituted or unsubstituted benzoic acid is forexample 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

[0328] 2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate andhexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate are preferred.

[0329] The acrylate is for example ethyl α-cyano-β,β-diphenylacrylate,isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate orN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0330] The oxamide is for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide or its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide or mixtures of ortho- andpara-methoxy—disubstituted oxanilides or mixtures of o- andp-ethoxy-disubstituted oxanilides.

[0331] The 2-(2-hydroxyphenyl)-1,3,5-triazine is for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1 ,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazineor 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

[0332]2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine arepreferred.

[0333] The monobenzoate of resorcinol is for example the compound of theformula

[0334] The formamidine is for example the compound of the formula

[0335] The UV absorber is in particular a2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone or ahydroxyphenyltriazine.

[0336] The stabilizer mixture according to the present invention isuseful for stabilizing polyolefins against degradation induced by light,heat or oxidation. Examples of suitable polyolefins are shown in thefollowing.

[0337] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), highdensity and high molecular weight polyethylene (HDPE-HMW), high densityand ultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), branched low density polyethylene (BLDPE).

[0338] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0339] a) radical polymerisation (normally under high pressure and atelevated temperature).

[0340] b) catalytic polymerisation using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerisation medium. The catalysts can be used by themselves inthe polymerisation or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0341] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0342] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0343] The invention therefore also relates to a composition containinga polyolefin and the stabilizer mixture as described herein and to amethod for stabilizing a polyolefin against degradation induced bylight, heat or oxidation, which comprises incorporating into thepolyolefin the stabilizer mixture.

[0344] The polyolefins listed above under point 1 are preferred.Polyethylene and polypropylene as well as a polyethylene copolymer or apolypropylene copolymer are particularly preferred. The inventionfurthermore relates to a composition comprising a polyolefin and astabilizer mixture containing

[0345] (A) a sterically hindered amine compound selected from the groupconsisting of the compounds 13, 14, 36-a, 36-b, 36-d, 96-I, 96-II,100-A, 101-I, 105 and 106 as defined above;

[0346] (B) an organic salt of Ca, in particular Ca-stearate, or aninorganic salt of Ca; and

[0347] (C) an organic salt of Mg, an inorganic salt of Mg, an organicsalt of Zn or an inorganic salt of Zn;

[0348] with the proviso that the polyolefin is polypropylene, whencomponent (A) of the stabilizer mixture is the compound 96-I, 96-II or100-A.

[0349] The components (A), (B), (C) and optionally (D1) and/or (D2) maybe added to the polyolefin either individually or mixed with oneanother.

[0350] The sterically hindered amine compound (component (A)) is presentin the polyolefin in an amount of preferably 0.01 to 5%, in particular0.01 to 1% or 0.05 to 1%, relative to the weight of the polyolefin.

[0351] The organic or inorganic salt of Ca (component (B)) is present inthe polyolefin in an amount of preferably 0.005 to 5%, in particular0.02 to 0.5%, relative to the weight of the polyolefin.

[0352] The organic or inorganic salt of Zn or Mg (component (C)) ispresent in the polyolefin in an amount of preferably 0.01 to 5%, inparticular 0.05 to 0.5%, relative to the weight of the polyolefin.

[0353] The pigment (component (D1)) is optionally present in thepolyolefin in an amount of preferably 0.01 to 10%, in particular 0.05 to1%, relative to the weight of the polyolefin.

[0354] The UV absorber (component (D2)) is optionally present in thepolyolefin in an amount of preferably 0.01 to 1%, in particular 0.05 to0.5%, relative to the weight of the polyolefin.

[0355] The total amount of component (D3) (the pigment in combinationwith the UV absorber) is preferably 0.01 to 10%, relative to the weightof the organic material. The weight ratio of the UV absorber to thepigment is for example 2:1 to 1:10.

[0356] When the pigment used is titanium dioxide in combination with anorganic pigment as described above, titanium dioxide is preferablypresent in the organic material in an amount of 0.01 to 5%, relative tothe weight of the organic material, and the organic pigment may bepresent in an amount of, for example, 0.01 to 2%, relative to the weightof the organic material.

[0357] The weight ratio of the components (A):(B) is preferably 20:1 to1:5.

[0358] The weight ratio of the components (A):(C) is preferably 20:1 to1:5.

[0359] The weight ratio of the components (A):(D1) is preferably 10:1 to1:10.

[0360] The weight ratio of the components (A):(D2) is preferably 20:1 to1:2.

[0361] The weight ratio of the components (A):(D3) is preferably 10:1 to1:10.

[0362] The above components can be incorporated into the polyolefin byknown methods, for example before or during shaping or by applying thedissolved or dispersed compounds to the polyolefin, if necessary withsubsequent evaporation of the solvent. The components can be added tothe polyolefin in the form of a powder, granules or a masterbatch, whichcontains these components in, for example, a concentration of from 2.5to 25% by weight.

[0363] If desired, the components (A), (B), (C) and optionally (D1)and/or (D2) can be melt blended with each other before incorporation inthe polyolefin. They can be added to the polyolefin before or during thepolymerization or before the crosslinking.

[0364] The polyolefin stabilized according to this invention can be usedin a wide variety of forms, for example as films, fibres, tapes,moulding compositions, profiles or as binders for paints, adhesives orputties.

[0365] The stabilized polyolefin may additionally also contain variousconventional additives, for example:

[0366] 1. Antioxidants

[0367] 1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butyl-phenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

[0368] 1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-didodecylthiomethyl-4-nonylphenol.

[0369] 1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0370] 1.4. Tocopherols, for example α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).

[0371] 1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0372] 1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.

[0373] 1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0374] 1.8. Hydroxybenzvlated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5--methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0375] 1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0376] 1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0377] 1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calciumsalt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0378] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0379] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0380] 1.14. Esters ofD-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- orpolyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0381] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0382] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol,thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0383] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

[0384] 1.18. Ascorbic acid (vitamin C)

[0385] 1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, Bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyidiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyidiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines,2,3-di-hydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixtureof mono- und dialkylated tert-butyl/tert-octylphenothiazines, a mixtureof mono- und dialkylated tert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diamino-but-2-ene,N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

[0386] 2. UV absorbers and light stabilisers

[0387] Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

[0388] 3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine ,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)-oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl-hydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

[0389] 4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

[0390] 5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhy-droxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0391] 6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

[0392] 7. Thiosynergists, for example, dilauryl thiodipropionate ordistearyl thiodipropionate.

[0393] 8. Peroxide scavengers, for example esters of β-thiodipropionicacid, for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

[0394] 9. Basic co-stabilisers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example calcium stearate, zinc stearate, magnesium behenate,magnesium stearate, sodium ricinoleate and potassium palmitate, antimonypyrocatecholate or tin pyrocatecholate.

[0395] 10. Nucleating agents, for example, inorganic substances such astalcum, metal oxides such as titanium dioxide or magnesium oxide,phosphates, carbonates or sulfates of, preferably, alkaline earthmetals; organic compounds such as mono- or polycarboxylic acids and thesalts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate or sodium benzoate; polymericcompounds such as ionic copolymers (“ionomers”).

[0396] 11. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin,mica, barium sulfate, metal oxides and hydroxides, carbon black,graphite, wood flour and flours or fibers of other natural products,synthetic fibers.

[0397] 12. Other additives, for example, plasticisers, lubricants,emulsifiers, pigments, rheology additives, catalysts, flow-controlagents, optical brighteners, flameproofing agents, antistatic agents andblowing agents.

[0398] 13. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No.5,175,312, U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643,DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0399] Particularly preferred conventional additives are those listedabove under items 1 and/or 4.

[0400] Also the compound of the formula

[0401] is one of the preferred conventional additives which mayadditionally be incorporated into the polyolefin to be stabilized.

[0402] The weight ratio of the total amount of components (A), (B), (C)and optionally (D1) and/or (D2) to the total amount of the conventionaladditives can be, for example, 100:1 to 1:100.

[0403] The examples below illustrate the invention in greater detail.All percentages and parts are by weight, unless stated otherwise.

[0404] Sterically hindered amine compounds used in the followingExamples 1 to 3:

[0405] (For the polymeric compounds, the mean degree of polymerizationis indicated in each case.)

[0406] Compound 13:

[0407] (®Tinuvin 770)

[0408] Compound 36-d:

[0409] (®Sanduvor PR-31)

[0410] Compound 81:

[0411] ®Tinuvin 622)

[0412] with m₁ being 5.1.

[0413] Compound 84-1:

[0414] (®Chimassorb 944)

[0415] with m₄ being 4.5.

[0416] Mixture of the compounds 96-I and 96-II:

[0417] (Preferably ®Hostavin N30)

[0418] with m₁₆ being 3.9 and m₁₆* being 4.2 and the weight ratio of(96-I) to (96-II) being 4:1.

[0419] Compound 100-A:

[0420] (®Uvasorb HA88 (Chemical Abstracts CAS No. 136 504-96-6)) Aproduct obtainable by reacting an intermediate product, obtained byreaction of a polyamine of the formula (100 a-I) with cyanuric chloride,with a compound of the formula (100b-I).

[0421]

[0422] Compound 101-1:

[0423] (Preferably ®Uvasil 299)

[0424] with m₂₁ being 5.8.

[0425] Compound 105:

[0426] (®Goodrite UV 3150)

[0427] Compound 106:

[0428] (®Goodrite UV 3159)

EXAMPLE 1

[0429] Light stabilization of injection molded 2 mm polypropyleneplaques.

[0430] 100 parts of polypropylene powder (melt flow index: ˜2.4 g/10 minat 230° C and 2160 g) are blended in a barrel mixer with 0.05 parts ofpentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],0.05 parts of tris[2,4-di-tert-butylphenyl] phosphite, and thestabilizer system indicated in Tables 1 to 3. Then, the blend iscompounded in an extruder at temperatures of 200°- 220° C. The granulesobtained on extrusion and granulation are transformed into 2 mm thickplaques at 240°-260° C. in an automatic injection molding machine.

[0431] The plaques are mounted on sample holders and subjected tonatural weathering in Florida (45° South, direct, approximately 140kLy/year). Periodically, the carbonyl content of the samples is measuredwith an infrared spectrophotometer. The exposure time corresponding toformation of a carbonyl absorbance of 0.5 is a measure for theefficiency of the stabilizer system.

[0432] The values obtained are summarized in Tables 1 to 3.

[0433] The synergistic effect of the two coadditivs ((1) and (2)) isdetermined by a comparison of the calculated T_(0.5) value with theactually measured T_(0.5) value. The T_(0.5) values are calculated onthe basis of the additivity law (B. Ranby and J. F. Rabek;Photodegradation, Photooxidation and Photostabilization of Polymers,Principles and Applications, John Wiley & Sons, London, New York,Sydney, Toronto, 1975, pages 418 and 419) according to the followingequation:${{Expected}\quad {stabilizing}\quad {activity}} = \frac{{{Stabilizing}\quad {activity}\quad {of}\quad 100\quad \% (1)} + {{stabilizing}\quad {activity}\quad {of}\quad 100\% \quad (2)}}{2}$

[0434] There is a synergistic effect for the two coadditivs in question,when T_(0.5 measured)>T_(0.5 calculated). TABLE 1 Sterically hinderedamine compound: 0.1% of the compound 81 T_(0.5 measured)T_(0.5 calculated) Coadditiv (kLy) (kLy) 0.1% of Ca-oxide 63 0.1% ofZn-hydroxide-carbonate 81 0.05% of Zn-hydroxide-carbonate + 86 72 0.05%of Ca-oxide

[0435] TABLE 2 Sterically hindered amine compound: 0.1% of the compound84-1 T_(0.5 measured) T_(0.5 calculated) Coadditiv (kLy) (kLy) 0.1% ofCa-stearate  88 0.1% of Ca-oxide 150 0.1% of hydrotalcite (® DHT-4A) 1440.1% of Zn-hydroxide-carbonate 136 0.05% of Ca-oxide + 180 147 0.05% ofhydrotalcite (® DHT-4A) 0.05% of Zn-hydroxide-carbonate + 168 112 0.05%of Ca-stearate 0.05% of Zn-hydroxide-carbonate + 172 143 0.05% ofCa-oxide

[0436] TABLE 3 Sterically hindered amine compound: 0.05% of the compound81 UV absorber: 0.05% of the compound of the formula

T_(0.5) measured T_(0.5) calculated Coadditiv (kLy) (kLy) 0.1% ofCa-stearate 136 0.1% of Ca-oxide 102 0.1% of Ca-hydroxide 149 0.1% ofhydrotalcite (® DHT-4A) 127 0.1% of Zn-hydroxide-carbonate 121 0.1% ofMg-stearate 216 0.1% of Zn-stearate 200 0.1% of Mg-acetylacetonate 2020.1% of Mg-oxide 176 0.1% of Zn-oxide  70 0.1% of Mg-hydroxide 146 0.1%of dolomite (® Microdol Super)  77 0.1% of Zn-acetylacetonate  68 0.05%of hydrotalcite (® DHT-4A) + 116 114.5 0.05% of Ca-oxide 0.05% ofZn-hydroxide-carbonate + 182 128.5 0.05% of Ca-stearate 0.05% ofZn-hydroxide-carbonate + 175 111.5 0.05% of Ca-oxide 0.05% of dolomite(® Microdol Super) + 112 106.5 0.05% of Ca-stearate 0.05% ofMg-stearate + 252 159 0.05% of Ca-oxide 0.05% of Mg-stearate + 222 182.50.05% of Ca-hydroxide 0.05% of Zn-stearate + 168 151 0.05% of Ca-oxide0.05% of Mg-acetylacetonate + 240 152 0.05% of Ca-oxide 0.05% ofMg-acetylacetonate + 248 175.5 0.05% of Ca-hydroxide 0.05% ofZn-acetylacetonate +  97 85 0.05% of Ca-oxide 0.05% ofZn-acetylacetonate + 126 108.5 0.05% of Ca-hydroxide 0.05% of Mg-oxide +148 139 0.05% of Ca-oxide 0.05% of Zn-oxide +  89 86 0.05% of Ca-oxide0.05% of Ca-oxide + 137 124 0.05% of Mg-hydroxide

EXAMPLE 2

[0437] Light stabilization of polypropylene tapes.

[0438] 100 parts of polypropylene powder (melt flow index: 2 g/10 min at230° C. and 2160 g) are blended in a barrel mixer with 0.05 parts ofpentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.05 parts oftris[2,4-di-tert-butylphenyl] phosphite and the stabilizer systemindicated in Table 4. Then, the blend is compounded in an extruder attemperatures of 180°- 220° C. The granules obtained on extrusion andgranulation are transformed into films at 220°-260° C. in a secondextruder equipped with a flat sheet die. The films are cut into ribbonswhich are drawn to achieve a stretch ratio of 1:6. The tapes obtainedwith this procedure are finally 50 μm thick and 2.5 mm wide.

[0439] The tapes are mounted without tension on sample holders andexposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C.,without water-spraying). Periodically, the tensile strength of theexposed tapes is measured. The exposure time corresponding to a loss of50% (T₅₀) of the initial tensile strength is a measure for theefficiency of the stabilizer system.

[0440] The values obtained are summarized in Table 4.

[0441] The determination of the synergistic effect of the two coadditivsis carried out as described in Example 1. TABLE 4 0.4% of titaniumdioxide (rutile) T_(50 measured) (hours to 50% retained tensilestrength) 0.05% of Ca-stear- ate + 0.05% of 0.1% of Sterically hinderedhydrotalcite 0.1% of hydrotalcite amine compound (® DHT-4A) Ca-stearate(® DHT-4A) T_(50 calculated) 0.05% of compound 13 3360 2150 1920 20350.10% of compound 13 7600 5600 4300 4950 0.20% of compound 13 14500 13500  10000  11750 

EXAMPLE 3

[0442] Light stabilization of compression molded 0.5 mm polypropylenecopolymer films

[0443] 100 parts of unstabilized polypropylene powder (melt flow index:˜6 g/10 min at 230° C. and 2160 g) are homogenized at 200° C. for 10 minin a Brabender plastograph with 0.05 parts ofpentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],0.10 parts of tris[2,4-di-tert-butylphenyl] phosphite, and thestabilizer system indicated in Tables 5 to 8. The material thus obtainedis compression molded in a laboratory press between two aluminum foilsfor 6 min at 260° C. to a 0.5 mm thick film which is cooled immediatelyto room temperature in a water-cooled press. Samples of 60 mm×25 mm arecut out of these 0.5 mm films and exposed in a WEATHER-OMETER Ci 65(black panel temperature 63±2° C., without water-spraying).Periodically, these samples are removed from the exposure apparatus andtheir carbonyl content is measured with an infrared spectrophotometer.The exposure time corresponding to formation of a carbonyl absorbance of0.1 is a measure for the efficiency of the stabilizer system. The valuesobtained are summarized in Tables 5 to 8. TABLE 5 0.1% of Ca-stearate,0.1% of Mg-stearate and 0.1% of the compound of the formula

0.1% of sterically hindered amine T_(0.1) compound (h) Compound 101-I3680 Compound 100-A 3200 Mixture of compounds 96-I and 96-II 2480Compound 105 2920 Compound 106 2600 Compound 36-d 3080

[0444] TABLE 6 0.1% of Ca-stearate, 0.1% of hydrotalcite (® DHT-4A) and0.1% of the compound of the formula

0.1% of sterically hindered amine T_(0.1) compound (h) Compound 101-I3680 Compound 100-A 3460 Compound 106 4400

[0445] TABLE 7 0.1% of Ca-stearate, 0.1% of Mg-stearate and 0.5% of TiO₂(rutile) 0.1% of sterically hindered amine T_(0.1) compound (h) Compound101-I 4530 Compound 100-A 3340 Compound 105 3280 Compound 106 3320Compound 36-d 3340

[0446] TABLE 8 0.1% of Ca-stearate, 0.1% of hydrotalcite (® DHT-4A) and0.1% of TiO₂ (rutile) 0.1% of sterically hindered amine T_(0.1) compound(h) Compound 101-I 4120 Compound 100-A 4080 Compound 105 3905 Compound106 3955

1. A stabilizer mixture containing (A) a sterically hindered aminecompound, (B) an organic salt of Ca or an inorganic salt of Ca and (C)an organic salt of Mg, an inorganic salt of Mg, an organic salt of Zn oran inorganic salt of Zn; with the proviso that component (C) isMg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite, whencomponent (B) is calcium stearate.
 2. A stabilizer mixture according toclaim 1 wherein the sterically hindered amine compound corresponds to acompound containing at least one group of the formula (I) or (II)

in which G is hydrogen or methyl, and G₁ and G₂, independently of oneanother, are hydrogen, methyl or together are a substituent ═O.
 3. Astabilizer mixture according to claim 1, wherein the sterically hinderedamine compound is

with m₁ being 5.1;

with m₄ being 4.5;

a product obtainable by reacting an intermediate product, obtained byreaction of a polyamine of the formula (100a-I) with cyanuric chloride,with a compound of the formula (100-I),

with m₂₁ being 5.8;


4. A stabilizer mixture according to claim 1 wherein the organic salt ofCa is Ca-stearate, Ca-lactate or Ca-stearoyl-lactate and the inorganicsalt of Ca is Ca-oxide or Ca-hydroxide.
 5. A stabilizer mixtureaccording to claim 1 wherein component (C) is hydrotalcite, dolomite,Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, Zn-oxide, Mg-oxide,Zn-hydroxide, Mg-hydroxide, Zn-stearate, Mg-stearate, Zn-laurate,Mg-laurate, Zn-acetylacetonate, Mg-acetylacetonate, Zn-acetate orMg-acetate.
 6. A stabilizer mixture according to claim 1, whereincomponent (B) is Ca oxide and component (C) is Mg stearate, component(B) is Ca oxide and component (C) is Zn stearate, component (B) is Caoxide and component (C) is hydrotalcite, component (B) is Ca hydroxideand component (C) is Mg stearate, or component (B) is Ca hydroxide andcomponent (C) is Zn stearate.
 7. A stabilizer mixture according to claim1, containing additionally (D1) a pigment or (D2) an UV absorber or (D3)a pigment and an UV absorber.
 8. A stabilizer mixture according to claim7 wherein the pigment is titanium dioxide, zinc oxide, carbon black,cadmium sulfide, cadmium selenide, chromium oxide, iron oxide, leadoxide, an azo pigment, an anthraquinone, a phthalocyanine, atetrachloroisoindolinone, a quinacridone, an isoindoline, a perylene ora pyrrolopyrrole.
 9. A stabilizer mixture according to claim 7 whereinthe UV absorber is a 2-(2′-hydroxyphenyl)benzotriazole, a2-hydroxybenzophenone, an ester of substituted or unsubstituted benzoicacid, an acrylate, an oxamide, a 2-(2-hydroxyphenyl)-1,3,5-triazine, amonobenzoate of resorcinoi or a formamidine.
 10. A compositioncomprising a polyolefin and a stabilizer mixture according to claim 1.11. A composition according to claim 10 wherein the polyolefin ispolyethylene, polypropylene, a polyethylene copolymer or a polypropylenecopolymer.
 12. A composition comprising a polyolefin and a stabilizermixture containing (A) a sterically hindered amine compound selectedfrom the group consisting of the compounds 13, 14, 36-a, 36-b, 36-d,96-I, 96-II, 100-A, 101-I, 105 and 106 as defined in claim 3; (B) anorganic salt of Ca or an inorganic salt of Ca; and (C) an organic saltof Mg, an inorganic salt of Mg, an organic salt of Zn or an inorganicsalt of Zn; with the proviso that the polyolefin is polypropylene, whencomponent (A) of the stabilizer mixture is the compound 96-I, 96-II or100-A.
 13. A method for stabilizing a polyolefin against degradationinduced by light, heat or oxidation, which comprises incorporating intothe polyolefin a stabilizer mixture according to claim 1.